Halbsandwich-Komplexe der Elemente Titan und Zirconium mit dem (Diisopropylaminoethyl) cyclopentadienyl-Ligand: Molekülstruktur von [(C 5H 4CH 2CH 2N(H) iPr 2)ZrCl 3] +Cl −·2CH 3OH

Abstract

The synthesis of titanium and zirconium complexes with the donor functionalized 2-(N,N-diisopropylaminoethyl)cyclopentadienyl (Cp N) ligand is described. The reaction of TiCl 4 with (C 5H 4CH 2CH 2N iPr 2)Li leads to the formation of the highly moisture-sensitive half-sandwich complex (C 5H 4CH 2CH 2N iPr 2)TiCl 3 ( 1), which easily forms a coordination polymer. Complex 1 reacts with one equivalent of HCl under protonation of the amino group to give the monomeric hydrochloride [(C 5H 4CH 2CH 2N(H) iPr 2)TiCl 3] +Cl − ( 2), which shows excellent solubility in polar solvents. The compound (C 5H 4CH 2CH 2N iPr 2)Ti(NMe 2) 3 ( 3) is prepared by the reaction of Ti(NMe 2) 4 with one equivalent of C 5H 5CH 2CH 2N iPr 2 (Cp NH). Reaction of 3 with three equivalents of isopropanol affords the isopropoxy derivative (C 5H 4CH 2CH 2N iPr 2)Ti(O iPr) 3 ( 4) in quantitative yield. The reaction of (C 5H 4CH 2C 2N iPr 2)Li with Me 3SiCl leads to the formation of the Cp N-transfer reagent (C 5H 4CH 2CH 2N iPr 2)SiMe 3 ( 5). The polymeric zirconium compound [(C 5H 4CH 2CH 2N iPr 2)ZrCl 3] x ( 6) is synthesized by the reaction of 5 with ZrCl 4. 6 reacts with one equivalent of HCl under protonation of the amino group to give the monomeric air- and moisture-stable hydrochloride [(C 5H 4CH 2CH 2N(H) iPr 2)ZrCl 3] +Cl −·2CH 3OH ( 7). The structure of 7 has been determined by single-crystal X-ray diffractometry. The reaction of 7 with water leads under exchange of the donor ligands to the formation of the air- and water-stable hydrochloride [(C 5H 4CH 2CH 2N(H) iPr 2)ZrCl 3] +Cl −·2H 2O ( 8). The compound (C 5H 4CH 2CH 2N iPr 2)Zr(NMe 2) 3 ( 9) is prepared by the reaction of Zr(NMe 2) 4 with one equivalent of C 5H 5CH 2CH 2N iPr 2 in nearly quantitative yield.